JP2018150485A - Clathrate compound - Google Patents
Clathrate compound Download PDFInfo
- Publication number
- JP2018150485A JP2018150485A JP2017049398A JP2017049398A JP2018150485A JP 2018150485 A JP2018150485 A JP 2018150485A JP 2017049398 A JP2017049398 A JP 2017049398A JP 2017049398 A JP2017049398 A JP 2017049398A JP 2018150485 A JP2018150485 A JP 2018150485A
- Authority
- JP
- Japan
- Prior art keywords
- group
- imidazole
- epoxy
- compound
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 95
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims abstract description 54
- -1 cyclic amine Chemical class 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000004593 Epoxy Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000002462 imidazolines Chemical class 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 27
- 150000003839 salts Chemical class 0.000 abstract description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 57
- 238000002441 X-ray diffraction Methods 0.000 description 39
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 16
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000013585 weight reducing agent Substances 0.000 description 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 7
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 210000003000 inclusion body Anatomy 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 3
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003828 azulenyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QJIMTLTYXBDJFC-UHFFFAOYSA-N (4-methylphenyl)-diphenylphosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJIMTLTYXBDJFC-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- URFNSYWAGGETFK-UHFFFAOYSA-N 1,2-bis(4-hydroxyphenyl)ethane Natural products C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- ADQQGJLCEXHTRW-UHFFFAOYSA-N 1-(dimethylamino)hexan-1-ol Chemical compound CCCCCC(O)N(C)C ADQQGJLCEXHTRW-UHFFFAOYSA-N 0.000 description 1
- QJAMEPRRHVBWKX-UHFFFAOYSA-N 1-[2-[2-(dimethylamino)ethoxy]ethoxy]ethanol Chemical compound CC(O)OCCOCCN(C)C QJAMEPRRHVBWKX-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DIHAURBCYGTGCV-UHFFFAOYSA-N xi-4,5-Dihydro-2,4(5)-dimethyl-1H-imidazole Chemical compound CC1CN=C(C)N1 DIHAURBCYGTGCV-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、新規な包接化合物、該包接化合物からなる硬化剤又は硬化触媒、該硬化剤又は硬化触媒を用いた硬化樹脂形成用組成物、該硬化樹脂形成用組成物を用いた硬化樹脂の製造方法、及び該製造方法により得られた硬化樹脂に関する。 The present invention relates to a novel clathrate compound, a curing agent or a curing catalyst comprising the clathrate compound, a cured resin-forming composition using the curing agent or the curing catalyst, and a cured resin using the cured resin-forming composition. And a cured resin obtained by the production method.
エポキシ樹脂は、優れた機械特性、熱特性を有するため様々な分野で広く用いられている。かかるエポキシ樹脂を硬化させるための硬化剤又は硬化触媒として、アミン類やイミダゾールが用いられているが、エポキシ樹脂とこれら硬化剤又は硬化触媒との混合液は、硬化の開始が早く、一液安定性が極めて悪いという問題がある。 Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties. As curing agents or curing catalysts for curing such epoxy resins, amines and imidazoles are used, but the liquid mixture of epoxy resins and these curing agents or curing catalysts has a rapid onset of curing and is stable in one liquid. There is a problem that the nature is extremely bad.
そこで、硬化剤又は硬化触媒として、イミダゾールにヒドロキシ安息香酸を付加したイミダゾール酸付加塩を用いること（特許文献１参照。）や、テトラキスフェノール系化合物（例えば、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン（以下、ポリフェノール系化合物という。）とイミダゾールとの包接体を用いること（特許文献２参照。））が提案されている。かかるイミダゾール酸付加塩や包接体は、一定の効果を奏するものであるが、硬化剤又は硬化触媒１モルの重量が、イミダゾールと対になる安息香酸やポリフェノール系化合物分増加する。そのため、重量当たりの硬化能が低下することになる。 Therefore, as a curing agent or a curing catalyst, an imidazolic acid addition salt obtained by adding hydroxybenzoic acid to imidazole (see Patent Document 1) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis ( The use of an inclusion body of 4-hydroxyphenyl) ethane (hereinafter referred to as a polyphenol compound) and imidazole has been proposed (see Patent Document 2). Such an imidazolic acid addition salt or clathrate has a certain effect, but the weight of 1 mol of the curing agent or curing catalyst is increased by the amount of benzoic acid or polyphenolic compound paired with imidazole. For this reason, the curability per weight is reduced.
本発明の課題は、従来のイミダゾール付加塩や包接体よりも、重量当たりの硬化能が高い硬化剤又は硬化触媒を提供することにある。 An object of the present invention is to provide a curing agent or a curing catalyst having a higher curability per weight than conventional imidazole addition salts and clathrates.
本発明者らは、上記課題を解決すべく鋭意研究した結果、１Ｈ−イミダゾール−４，５−ジカルボン酸をホスト化合物として用いて、アミン類やイミダゾールを包接化することにより、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by including amines and imidazoles using 1H-imidazole-4,5-dicarboxylic acid as a host compound. The present inventors have found that this can be done and have completed the present invention.
すなわち、本発明は、以下の発明に関する。
（１）下記の成分（１）および成分（２）を含有する包接化合物。
成分（１）：１Ｈ−イミダゾール−４，５−ジカルボン酸；
成分（２）：脂肪族アミン類、環状アミン類、芳香族アミン類、イミダゾリン系化合物及びイミダゾール系化合物からなる群より選ばれる少なくとも１種
（２）（１）に記載の包接化合物からなるエポキシ樹脂用硬化剤又は硬化触媒。
（３）（１）に記載の包接化合物と、エポキシ樹脂とを含有するエポキシ硬化樹脂形成用組成物。
（４）（３）に記載のエポキシ硬化樹脂形成用組成物を加熱処理することにより硬化して、エポキシ硬化樹脂を製造する方法。
（５）（３）に記載のエポキシ硬化樹脂形成用組成物を加熱処理することにより硬化して得られたエポキシ硬化樹脂。
That is, the present invention relates to the following inventions.
(1) An inclusion compound containing the following component (1) and component (2).
Component (1): 1H-imidazole-4,5-dicarboxylic acid;
Component (2): epoxy comprising at least one clathrate compound selected from the group consisting of aliphatic amines, cyclic amines, aromatic amines, imidazoline compounds and imidazole compounds (2) (1) Curing agent for resin or curing catalyst.
(3) A composition for forming an epoxy cured resin, comprising the clathrate compound according to (1) and an epoxy resin.
(4) A method for producing an epoxy cured resin by curing the composition for forming an epoxy cured resin according to (3) by heat treatment.
(5) An epoxy cured resin obtained by curing the composition for forming an epoxy cured resin according to (3) by heat treatment.
本発明の包接化合物は、低温での硬化反応を抑制して、一液安定性の向上を図ると共に、加熱処理を施すことにより、効果的に樹脂を硬化させることができる硬化剤又は硬化触媒（包接化合物）である。また、本発明の包接化合物は、ゲスト化合物のアミン類やイミダゾールと併せて、ホスト化合物である１Ｈ−イミダゾール−４，５−ジカルボン酸も硬化剤又は硬化触媒として機能するため、重量当たりの硬化能が向上した硬化剤又は硬化触媒である。 The clathrate compound of the present invention suppresses a curing reaction at a low temperature to improve one-component stability and can cure a resin effectively by heat treatment. (Inclusion compound). In addition, since the inclusion compound of the present invention functions as a curing agent or a curing catalyst, 1H-imidazole-4,5-dicarboxylic acid, which is a host compound, together with amines and imidazoles of guest compounds, curing per weight It is a curing agent or curing catalyst with improved performance.
〔成分（１）〕
本発明の包接化合物は、第一成分（以下、「成分（１）」と言うことがある。）として、１Ｈ−イミダゾール−４，５−ジカルボン酸を用いる。
[Ingredient (1)]
The inclusion compound of the present invention uses 1H-imidazole-4,5-dicarboxylic acid as the first component (hereinafter sometimes referred to as “component (1)”).
〔成分（２）〕
本発明の包接化合物は、第二成分（「成分（２）」と言うことがある。）として、脂肪族アミン類、環状アミン類、芳香族アミン類、イミダゾリン系化合物及びイミダゾール系化合物からなる群より選ばれる少なくとも１種を用いる。
脂肪族アミン類、環状アミン類、芳香族アミン類、イミダゾリン系化合物及びイミダゾール系化合物は、エポキシ基と反応してエポキシ樹脂を硬化させる化合物であれば、特に制限なく用いることができる。
脂肪族アミン類は、具体的には、以下の化合物を挙げることができる。
エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジプロピレンジアミン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、トリメチルヘキサメチレンジアミン、ペンタンジアミン、ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサメチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、ビス（２−ジメチルアミノエチル）エーテル、ジメチルアミノエトキシエトキシエタノール、ジメチルアミノヘキサノール、３-アミノプロピルトリエトキシシラン、ジイソプロピルエチルアミン等；
[Ingredient (2)]
The clathrate compound of the present invention comprises aliphatic amines, cyclic amines, aromatic amines, imidazoline compounds and imidazole compounds as the second component (sometimes referred to as “component (2)”). At least one selected from the group is used.
Aliphatic amines, cyclic amines, aromatic amines, imidazoline compounds and imidazole compounds can be used without particular limitation as long as they are compounds that react with an epoxy group to cure an epoxy resin.
Specific examples of the aliphatic amines include the following compounds.
Ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, pentanediamine, pentamethyldiethylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethyl Cyclohexylamine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol, 3-aminopropyltriethoxysilane, di Isopropylethylamine and the like;
環状アミン類は、具体的には、以下の化合物を挙げることができる。
ピペリジン、ピペラジン、１，４−ジアザビシクロ（２，２，２）オクタン（トリエチレンジアミン）、メチルモルホリン、エチルモルホリン、Ｎ，Ｎ’，Ｎ”−トリス（ジメチルアミノプロピル）ヘキサヒドロ−ｓ−トリアジン、Ｎ−アミノエチルピペラジン、トリメチルアミノエチルピペラジン、Ｎ，Ｎ’−ジメチルピペラジン、１，８−ジアザビシクロ（４，５，０）−７−ウンデセン等；
Specific examples of the cyclic amines include the following compounds.
Piperidine, piperazine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), methylmorpholine, ethylmorpholine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, N— Aminoethylpiperazine, trimethylaminoethylpiperazine, N, N′-dimethylpiperazine, 1,8-diazabicyclo (4,5,0) -7-undecene, etc .;
芳香族アミン類は、具体的には、以下の化合物を挙げることができる。
ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ジアミノジフェニルメタン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、ベンジルメチルアミン、ジメチルベンジルアミン、ｍ−キシレンジアミン、ピリジン、ピコリン等；
Specific examples of the aromatic amines include the following compounds.
o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine , Picoline, etc .;
イミダゾリン系化合物は、具体的には、以下の化合物を挙げることができる。
２−メチルイミダゾリン、２−フェニルイミダゾリン、２−ウンデシルイミダゾリン、２−ヘプタデシルイミダゾリン、２−エチルイミダゾリン、２−ｉ−プロピルイミダゾリン、２，４−ジメチルイミダゾリン、２−フェニル−４−メチルイミダゾリン等；
Specific examples of the imidazoline-based compound include the following compounds.
2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-ethylimidazoline, 2-i-propylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, etc. ;
イミダゾール系化合物は、具体的には、以下の式（Ｉ）で表されるイミダゾール化合物が該当する。 Specifically, the imidazole compound corresponds to an imidazole compound represented by the following formula (I).
式（Ｉ）中、Ｒ１は、水素原子、無置換若しくは置換基を有するＣ１〜２０アルキル基、又は無置換若しくは置換基を有するＣ６〜１０アリール基を表す。Ｒ２〜Ｒ４は、それぞれ独立に、水素原子、ハロゲノ基、無置換若しくは置換基を有するＣ１〜２０アルキル基、無置換若しくは置換基を有するＣ６〜１０アリール基、ニトロ基、又はシアノ基を表す。 In formula (I), R 1 represents a hydrogen atom, an unsubstituted or substituted C1-20 alkyl group, or an unsubstituted or substituted C6-10 aryl group. R 2 to R 4 each independently represent a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-20 alkyl group, an unsubstituted or substituted C6-10 aryl group, a nitro group, or a cyano group. Represent.
Ｒ１における「Ｃ１〜２０アルキル基」は、直鎖であってもよいし、分岐鎖であってもよい。「Ｃ１〜２０アルキル基」としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｉ−プロピル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｉ−ペンチル基、ネオペンチル基、２−メチルブチル基、２，２−ジメチルプロピル基、ｉ−ヘキシル基、ノニル基、ｉ−ノニル基、デシル基、ラウリル基、トリデシル基、ミリスチル基、ペンタデシル基、パルミチル基、ヘプタデシル基、ステアリル基等を挙げることができる。 The “C1-20 alkyl group” in R 1 may be linear or branched. Examples of the “C1-20 alkyl group” include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, and s-butyl group. T-butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, i-hexyl group, nonyl group, i-nonyl group, decyl group, lauryl group, tridecyl group, myristyl Group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.
「Ｃ１〜２０アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１〜６アルコキシ基、Ｃ３〜８シクロアルキル基、Ｃ６〜１０アリール基、置換シリル基、又はシアノ基が好ましい。
「ハロゲノ基」としては、フルオロ基、クロロ基、ブロモ基、イオド基等を挙げることができる。
「Ｃ１〜６アルコキシ基」としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｎ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基、ｉ−プロポキシ基、ｉ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ｉ−ヘキシルオキシ基等を挙げることができる。
「Ｃ３〜８シクロアルキル基」としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などのＣ３〜８シクロアルキル基等を挙げることができる。
「Ｃ６〜１０アリール基」としては、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基等を挙げることができる。
「置換シリル基」としては、トリメチルシリル基、トリエチルシリル基、ジメチル（１−メチルエチル）シリル基、（１，１−ジメチルエチル）ジメチルシリル基等のＣ１〜６アルキル基置換シリル基；トリメトキシシリル基、トリエトキシシリル基等のＣ１〜６アルコキシ基置換シリル基；等を挙げることができる。
The substituent on the “C1-20 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, a substituted silyl group, or a cyano group.
Examples of the “halogeno group” include a fluoro group, a chloro group, a bromo group, and an iodo group.
Examples of the “C1-6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, i-propoxy group, i-butoxy group, s- A butoxy group, a t-butoxy group, an i-hexyloxy group, and the like can be given.
Examples of the “C3-8 cycloalkyl group” include C3-8 cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the “C6-10 aryl group” include phenyl group, naphthyl group, azulenyl group, indenyl group, indanyl group, tetralinyl group and the like.
Examples of the “substituted silyl group” include trimethylsilyl group, triethylsilyl group, dimethyl (1-methylethyl) silyl group, C1,6 alkyl group-substituted silyl group such as (1,1-dimethylethyl) dimethylsilyl group; Group, C1-6 alkoxy group-substituted silyl group such as triethoxysilyl group; and the like.
Ｒ１における「Ｃ６〜１０アリール基」は、単環および多環のいずれであってもよい。多環アリール基は、少なくとも一つの環が芳香環であれば、残りの環が飽和脂環、不飽和脂環または芳香環のいずれであってもよい。
Ｒ１における「Ｃ６〜１０アリール基」としては、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基などを挙げることができる。
The “C6-10 aryl group” in R 1 may be monocyclic or polycyclic. In the polycyclic aryl group, if at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
Examples of the “C6-10 aryl group” in R 1 include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
「Ｃ６〜１０アリール基」上の置換基としては、ハロゲノ基、Ｃ１〜６アルキル基、水酸基、Ｃ１〜６アルコキシ基、Ｃ１〜６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。
「ハロゲノ基」、「Ｃ１〜６アルコキシ基」としては、前記Ｒ１において例示したそれらと同じものを挙げることができる。
「Ｃ１〜６アルキル基」としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｉ−プロピル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｉ−ヘキシル基等を挙げることができる。
「Ｃ１〜６ハロアルコキシ基」としては、トリフルオロメトキシ基、２−クロロ−ｎ−プロポキシ基、２，３−ジクロロブトキシ基等を挙げることができる。
Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
Examples of the “halogeno group” and “C1-6 alkoxy group” include the same as those exemplified in the above R 1 .
As the “C1-6 alkyl group”, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group , T-butyl group, i-hexyl group and the like.
Examples of the “C 1-6 haloalkoxy group” include trifluoromethoxy group, 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group and the like.
Ｒ２〜Ｒ４における、「ハロゲノ基」、「Ｃ１〜２０アルキル基」、及び「Ｃ６〜１０アリール基」としては、前記Ｒ１において例示したそれらと同じものを挙げることができる。
「Ｃ１〜２０アルキル基」上の置換基としては、ハロゲノ基、水酸基、Ｃ１〜６アルコキシ基、Ｃ３〜８シクロアルキル基、Ｃ６〜１０アリール基、置換シリル基、又はシアノ基が好ましい。
「Ｃ６〜１０アリール基」上の置換基としては、ハロゲノ基、Ｃ１〜６アルキル基、水酸基、Ｃ１〜６アルコキシ基、Ｃ１〜６ハロアルコキシ基、シアノ基、ニトロ基などを挙げることができる。
Examples of the “halogeno group”, “C1-20 alkyl group”, and “C6-10 aryl group” in R 2 to R 4 are the same as those exemplified in the above R 1 .
The substituent on the “C1-20 alkyl group” is preferably a halogeno group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, a substituted silyl group, or a cyano group.
Examples of the substituent on the “C6-10 aryl group” include halogeno group, C1-6 alkyl group, hydroxyl group, C1-6 alkoxy group, C1-6 haloalkoxy group, cyano group, nitro group and the like.
イミダゾール化合物としては、具体的には、イミダゾール、２−エチル−４−メチルイミダゾール、１−メチルイミダゾール、２−メチルイミダゾール、４−メチルイミダゾール、２−ヘプタデシルイミダゾール、２−ウンデシルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１，２−ジメチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾールなどを挙げることができる。 Specific examples of imidazole compounds include imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1- Benzyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5- Jihyd , And the like carboxymethyl methylimidazole.
〔包接化合物〕
「包接化合物」とは、２種又は３種以上の分子が共有結合以外の弱い結合により結合した化合物をいい、より好ましくは、２種又は３種以上の分子が共有結合以外の弱い結合により結合した結晶性化合物をいう。
本発明の包接化合物としては、成分（１）と、成分（２）とを含有する包接化合物であれば特に制限されるものではない。本発明の包接化合物は、溶媒等の第３成分を含んでもよく、該第３成分は、４０モル％以下であることが好ましく、２０モル％以下であることがさらに好ましく、１０モル％以下であることが特に好ましい。
本発明の包接化合物は、ポリエステル樹脂、エポキシ樹脂、エポキシ・ポリエステル樹脂、ウレタン樹脂等の樹脂硬化剤又は硬化触媒として使用することができ、特にエポキシ樹脂の硬化剤又は硬化触媒として好適に使用することができる。また、本発明の包接化合物は、溶媒に溶解した液状のものであってもよいが、（溶媒中で析出する）粉体状のものが好ましい。粉体状であることにより、例えば、粉体塗料に使用することができる。
[Inclusion compound]
The “inclusion compound” refers to a compound in which two or more molecules are bonded by a weak bond other than a covalent bond, and more preferably, two or more molecules are bonded by a weak bond other than a covalent bond. A bonded crystalline compound.
The clathrate compound of the present invention is not particularly limited as long as it is a clathrate compound containing the component (1) and the component (2). The clathrate compound of the present invention may contain a third component such as a solvent, and the third component is preferably 40 mol% or less, more preferably 20 mol% or less, and more preferably 10 mol% or less. It is particularly preferred that
The inclusion compound of the present invention can be used as a resin curing agent or curing catalyst for polyester resins, epoxy resins, epoxy / polyester resins, urethane resins, etc., and particularly preferably used as a curing agent or curing catalyst for epoxy resins. be able to. The clathrate compound of the present invention may be in the form of a liquid dissolved in a solvent, but is preferably in the form of a powder (deposited in the solvent). By being in a powder form, it can be used for, for example, a powder coating.
本発明の包接化合物は、成分（１）及び成分（２）を溶媒に添加後、必要に応じて攪拌しながら、加熱処理又は加熱還流処理を行い、再結晶させて析出させることにより得ることができる。また、溶媒への溶解のしやすさを考慮すると、成分（１）及び成分（２）をそれぞれ溶媒に溶解後、溶解液同士を混合することが好ましい。
溶媒としては、水、メタノール、エタノール、イソプロピルアルコール、酢酸エチル、酢酸メチル、ジエチルエーテル、ジメチルエーテル、テトラヒドロフラン、１，４−ジオキサン、アセトン、メチルエチルケトン、アセトニトリル、ベンゼン、トルエン、ヘキサン、クロロホルム、ジクロロメタン、四塩化炭素等を用いることができる。本発明の包接化合物の製造時における成分（１）及び成分（２）の添加割合としては、成分（１）１モルに対して、成分（２）が、０．１〜５．０モルであることが好ましく、０．５〜３．０モルであることがより好ましい。
生成物である包接化合物中の成分（１）と成分（２）のモル比は、特に制限はないが、１：１、１：２、２：１等適宜選択できる。
包接化合物の形成は、熱分析（ＴＧ及びＤＴＡ）、赤外吸収スペクトル（ＩＲ）、Ｘ線回折パターン（ＸＲＤ）、固体ＮＭＲスペクトル等により確認できる。また、包接化合物の組成は、熱分析、１Ｈ−ＮＭＲスペクトル、高速液体クロマトグラフィー（ＨＰＬＣ）、元素分析等により確認することができる。
The clathrate compound of the present invention is obtained by adding component (1) and component (2) to a solvent, then subjecting to heat treatment or heat reflux with stirring as necessary, recrystallizing and precipitating. Can do. In consideration of easiness of dissolution in a solvent, it is preferable to dissolve the components (1) and (2) in the solvent and then mix the solutions.
Solvents include water, methanol, ethanol, isopropyl alcohol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, benzene, toluene, hexane, chloroform, dichloromethane, tetrachloride. Carbon or the like can be used. As an addition ratio of the component (1) and the component (2) during the production of the clathrate compound of the present invention, the component (2) is 0.1 to 5.0 mol with respect to 1 mol of the component (1). It is preferable that it is 0.5 to 3.0 mol.
The molar ratio of the component (1) and the component (2) in the clathrate compound as a product is not particularly limited, but can be appropriately selected such as 1: 1, 1: 2, 2: 1.
Formation of the clathrate compound can be confirmed by thermal analysis (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction pattern (XRD), solid NMR spectrum, and the like. The composition of the clathrate compound can be confirmed by thermal analysis, 1 H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis or the like.
〔エポキシ硬化樹脂形成用組成物〕
また、本発明のエポキシ硬化樹脂形成用組成物としては、エポキシ樹脂と、上記本発明の包接化合物とを含有するものあれば特に制限されるものではない。
[Epoxy cured resin forming composition]
Further, the composition for forming an epoxy cured resin of the present invention is not particularly limited as long as it contains an epoxy resin and the inclusion compound of the present invention.
〔エポキシ樹脂〕
エポキシ樹脂としては、従来公知の各種ポリエポキシ化合物が使用でき、例えば、ビス（４−ヒドロキシフェニル）プロパンジグリシジルエーテル、ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパンジグリシジルエーテル、ビス（４−ヒドロキシフェニル）エタンジグリシジルエーテル、ビス（４−ヒドロキシフェニル）メタンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、フロログリシノールトリグリシジルエーテル、トリヒドロキシビフェニルトリグリシジルエーテル、テトラグリシジルベンゾフェノン、ビスレゾルシノールテトラグリシジルエーテル、テトラメチルビスフェノールＡジグリシジルエーテル、ビスフェノールＣジグリシジルエーテル、ビスフェノールヘキサフルオロプロパンジグリシジルエーテル、１，３−ビス〔１−（２，３−エポキシプロポキシ）−１−トリフルオロメチル−２，２，２−トリフルオロエチル〕ベンゼン、１，４−ビス〔１−（２，３−エポキシプロポキシ）−１−トリフルオロメチル−２，２，２−トリフルオロメチル〕ベンゼン、４，４′−ビス（２，３−エポキシプロポキシ）オクタフルオロビフェニル、フェノールノボラック型ビスエポキシ化合物などの芳香族系グリシジルエーテル化合物；アリサイクリックジエポキシ アセタール、アリサイクリックジエポキシ アジペート、アリサイクリックジエポキシ カルボキシレート、ビニルシクロヘキセンジオキシドなどの脂環式ポリエポキシ化合物；ジグリシジルフタレート、ジグリシジルテトラヒドロフタレート、ジグリシジルヘキサヒドロフタレート、ジメチルグリシジルフタレート、ジメチルグリシジルヘキサヒドロフタレート、ジグリシジル−ｐ−オキシベンゾエート、ジグリシジルシクロペンタン−１，３−ジカルボキシレート、ダイマー酸グリシジルエステルなどのグリシジルエステル化合物；ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジルアミノフェノール、テトラグリシジルジアミノジフェニルメタン、ジグリシジルトリブロモアニリンなどのグリシジルアミン化合物；ジグリシジルヒダントイン、グリシジルグリシドオキシアルキルヒダントイン、トリグリシジルイソシアヌレートなどの複素環式エポキシ化合物などを挙げることができる。
〔Epoxy resin〕
As the epoxy resin, various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propane diglycidyl ether, bis ( 4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether Tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane diglycidyl Ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2,3- Epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4′-bis (2,3-epoxypropoxy) octafluorobiphenyl, phenol novolac type bisepoxy compounds, and other aromatics Alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, and other alicyclic polyepoxy compounds; diglycidyl phthalate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthale Glycidyl ester compounds such as diglycidyl aniline, diglycidyl toluidine, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate Examples thereof include glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, and diglycidyltribromoaniline; and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate.
本発明のエポキシ硬化樹脂形成用組成物におけるエポキシ樹脂及び包接化合物の割合は、エポキシ樹脂のエポキシ環１モルに対して、包接化合物を０．０１〜１．０モル含有することが好ましく、０．１〜１．０モル含有することがより好ましく、０．３〜１．０モル含有することがさらに好ましい。 The ratio of the epoxy resin and the clathrate compound in the epoxy cured resin forming composition of the present invention preferably contains 0.01 to 1.0 mol of the clathrate compound relative to 1 mol of the epoxy ring of the epoxy resin. It is more preferable to contain 0.1-1.0 mol, and it is still more preferable to contain 0.3-1.0 mol.
また、本発明のエポキシ硬化樹脂形成用組成物は、エポキシ樹脂及び包接化合物を混合することにより製造することができるが、十分な混合状態が形成されるよう、通常、室温〜１００℃程度に加熱して混合する。エポキシ硬化樹脂の製造においては、このときの温度での一液安定性が重要となる。 Moreover, although the composition for epoxy cured resin formation of this invention can be manufactured by mixing an epoxy resin and a clathrate compound, it is normally about room temperature-about 100 degreeC so that sufficient mixing state may be formed. Mix by heating. In the production of an epoxy cured resin, the stability of one liquid at this temperature is important.
本発明の組成物には、上記の成分以外にも所望の特性を付与する目的で以下の成分を追加することができる。
（１）エポキシ樹脂用硬化触媒
本発明の組成物には、上記の本発明の硬化剤又は硬化触媒以外に、公知の硬化触媒を併用できる。
例えば、１，５−ジアザビシクロ［４．３．０］ノナ−５−エン、１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン、５，６−ジブチルアミノ−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン等の環状アミジン化合物；無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水マレイン酸、無水トリメリット酸等の酸無水物；１，４−ベンゾキノン、２，５−トルキノン、１，４−ナフトキノン、２，３−ジメチルベンゾキノン、２，６−ジメチルベンゾキノン、２，３−ジメトキシ−５−メチル−１，４ベンゾキノン、２，３−ジメトキシ−１，４−ベンゾキノン、フェニル−１，４−ベンゾキノン等のキノン化合物；トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の第三級アミン化合物；ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ｍ−キシレンジアミン等の芳香族アミン化合物；イミダゾール、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール等のイミダゾール化合物；トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニル（ｐ−トリル）ホスフィン等の有機ホスフィン化合物；等が挙げられる。
In addition to the above components, the following components can be added to the composition of the present invention for the purpose of imparting desired properties.
(1) Curing catalyst for epoxy resin In addition to the curing agent or curing catalyst of the present invention, a known curing catalyst can be used in combination with the composition of the present invention.
For example, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] Cyclic amidine compounds such as undec-7-ene; acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, trimellitic anhydride; 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1 , 4-quinone compounds such as phenyl-1,4-benzoquinone; triethylenediamine, benzyldimethylamine, triethanolamine, Tertiary amine compounds such as methylaminoethanol and tris (dimethylaminomethyl) phenol; aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and m-xylenediamine Compound; Imidazole compounds such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; And organic phosphine compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenyl (p-tolyl) phosphine;
（２）硬化剤
さらにエポキシ樹脂を硬化させるための公知の硬化剤を使用できる。例えば、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等の１分子中に２個のフェノール性水酸基を有する化合物；フェノールノボラック樹脂、クレゾールノボラック樹脂、クレゾールアラルキル樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、ナフトールアラルキル樹脂等の多価フェノール樹脂；等が挙げられる。
(2) Curing agent Further known curing agents for curing the epoxy resin can be used. For example, compounds having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F; phenol novolak resin, cresol novolak resin, cresol aralkyl resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene Polyphenol resin such as a type phenol resin and a naphthol aralkyl resin; and the like.
（３）フィラー
また、粘度や硬化物の物性を制御するためにフィラーを配合してもよい。フィラーとしては、絶縁性無機フィラーやウィスカー、樹脂フィラーを使用できる。絶縁性無機フィラーとしては、例えば、ガラス、シリカ、アルミナ、酸化チタン、カーボンブラック、マイカ、窒化ホウ素等が挙げられる。ウィスカーとしてはホウ酸アルミニウム、チタン酸アルミニウム、酸化亜鉛、珪酸カルシウム、硫酸マグネシウム、窒化ホウ素等が挙げられる。樹脂フィラーとしては、ポリウレタン樹脂、ポリイミド樹脂などを用いることができる。
その他にも、金、銀、銅、ニッケル、ハンダ等の金属粒子、及びカーボン等の導電フィラーも電子部品の接合用接着剤を構成する場合に使用できる。
(3) Filler In addition, a filler may be blended in order to control the viscosity and physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, or resin filler can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. A polyurethane resin, a polyimide resin, or the like can be used as the resin filler.
In addition, metal particles such as gold, silver, copper, nickel, solder, and conductive fillers such as carbon can also be used when constituting an adhesive for joining electronic components.
（４）その他の添加剤
また、本発明の目的とする所望の特性を阻害しない範囲で、離型剤、レベリング剤、シランカップリング剤、難燃剤、酸化防止剤、着色剤、シリコーン系可撓剤、イオントラップ剤等の公知の添加剤を配合できる。
(4) Other additives In addition, the release agent, leveling agent, silane coupling agent, flame retardant, antioxidant, colorant, silicone-based flexibility, as long as the desired properties of the present invention are not impaired. Known additives such as an agent and an ion trapping agent can be blended.
〔エポキシ硬化樹脂〕
本発明のエポキシ硬化樹脂の製造方法としては、上記エポキシ硬化樹脂形成用組成物を加熱処理して硬化させる方法であれば特に制限されるものではなく、通常、加熱処理の加熱温度としては、６０〜２５０℃であり、好ましくは、８０〜２００℃であり、かかる温度において短時間で硬化することが好ましい。
[Epoxy cured resin]
The method for producing the epoxy curable resin of the present invention is not particularly limited as long as it is a method of curing the epoxy curable resin-forming composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 It is -250 degreeC, Preferably, it is 80-200 degreeC, and it is preferable to harden | cure at this temperature for a short time.
〔使用用途〕
本発明の包接化合物は、潜在性に優れたエポキシ樹脂硬化剤又は硬化触媒である。これを含有するエポキシ硬化樹脂形成用組成物は、室温近辺で保管した場合は長期安定であり、硬化に際しては比較的低温で速やかに硬化させることができる。
本発明のエポキシ硬化樹脂形成用組成物の使用用途としては、特に制限されるものではなく、例えば、アンダーフィル、熱硬化性プリプレグ、注型材料、構造用接着剤、粉体塗料等を挙げることができる。特には、電子材料関連について、プリント基板用プリプレグ、半導体・電子部品用封止材、電子部品用接着剤、導電性接着剤、レジストインク、絶縁材料等を挙げることができる。
〔Use applications〕
The clathrate compound of the present invention is an epoxy resin curing agent or curing catalyst with excellent latency. The composition for forming an epoxy cured resin containing this is stable for a long time when stored near room temperature, and can be quickly cured at a relatively low temperature during curing.
The use of the composition for forming an epoxy curable resin of the present invention is not particularly limited, and examples thereof include underfill, thermosetting prepreg, casting material, structural adhesive, and powder coating. Can do. In particular, regarding electronic materials, prepregs for printed circuit boards, sealing materials for semiconductors and electronic components, adhesives for electronic components, conductive adhesives, resist inks, insulating materials, and the like can be given.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
（１）包接体の作製
[実施例１]
（１Ｈ−イミダゾール−４，５−ジカルボン酸と２―メチルイミダゾールから成る包接化合物）
フラスコに５．００ｇの１Ｈ−イミダゾール−４，５−ジカルボン酸を加えた後、２．６３ｇの２―メチルイミダゾール（以下、２ＭＺ）、及び溶媒としてメタノールを３０ｇ加え、撹拌しながら加熱還流を３時間行った。冷却後、ろ過、減圧乾燥を行うことで７．４８ｇの生成物を得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定より、１Ｈ−イミダゾール−４，５−ジカルボン酸と２ＭＺのモル比が１：１である包接化合物（以下、「包接化合物Ａ」と言うことがある。）であることを確認した。以下にそれらの測定結果を示した。
(1) Production of inclusion body
[Example 1]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and 2-methylimidazole)
After adding 5.00 g of 1H-imidazole-4,5-dicarboxylic acid to the flask, 2.63 g of 2-methylimidazole (hereinafter, 2MZ) and 30 g of methanol as a solvent were added, and the mixture was heated to reflux with stirring. Went for hours. After cooling, 7.48 g of product was obtained by filtration and drying under reduced pressure. From the XRD, TG-DSC and 1 H-NMR measurement, the obtained product was an inclusion compound (hereinafter referred to as “inclusion”) in which the molar ratio of 1H-imidazole-4,5-dicarboxylic acid to 2MZ was 1: 1. It was sometimes referred to as “Compound A”. The measurement results are shown below.
各スペクトルの測定条件は以下の通りである（他の実施例においても同様である。）
[ＸＲＤ測定]
装置：Ｕｌｔｉｍａ IV（リガク社製）
Ｘ線源：Ｃｕ ４０ｋＶ／４０ｍＡ
測定方法：集中法
フィルター：Ｋβフィルター
スキャン速度：５°／ｍｉｎ．
[ＴＧ−ＤＳＣ測定]
装置：ＴＧＡ−ＤＳＣ１（メトラー・トレド社製）
Ａｌ ＰＡＮ シール
測定温度範囲：室温〜５００℃
昇温速度：２０℃／ｍｉｎ
サンプル量：約３ｍｇ
[１Ｈ−ＮＭＲ測定]
装置：ＪＮＭ−ＡＬ４００（日本電子社製）
重溶媒：ＤＭＳＯ
積算回数：８回
The measurement conditions for each spectrum are as follows (the same applies to other examples).
[XRD measurement]
Device: Ultimate IV (manufactured by Rigaku Corporation)
X-ray source: Cu 40 kV / 40 mA
Measurement method: Concentration method Filter: Kβ filter Scan speed: 5 ° / min.
[TG-DSC measurement]
Apparatus: TGA-DSC1 (manufactured by METTLER TOLEDO)
Al PAN seal measurement temperature range: room temperature to 500 ° C
Temperature increase rate: 20 ° C / min
Sample amount: about 3mg
[1 H-NMR measurement]
Device: JNM-AL400 (manufactured by JEOL Ltd.)
Heavy solvent: DMSO
Integration count: 8 times
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが観測された（図１）。
(XRD measurement)
The diffraction pattern of the raw material disappeared and a new diffraction pattern was observed (FIG. 1).
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸では２９３℃、２ＭＺでは８９℃であるのに対し、包接化合物Ａは２４１℃であった。また重量減少に係るオンセット温度は１Ｈ−イミダゾール−４，５−ジカルボン酸では３０１℃、２ＭＺでは１６２℃であるのに対し、包接化合物Ａは２４０℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid, and 89 ° C. for 2 MZ, whereas inclusion compound A was 241 ° C. The onset temperature for weight reduction was 301 ° C. for 1H-imidazole-4,5-dicarboxylic acid, and 162 ° C. for 2MZ, while 240 ° C. for inclusion compound A.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸および２ＭＺに帰属されるピーク積分値から、モル比が１対１で包接化されていることが分かった。
(1 H-NMR measurement)
From the peak integral value attributed to 1H-imidazole-4,5-dicarboxylic acid and 2MZ, it was found that the molar ratio was 1: 1.
[実施例２]
（１Ｈ−イミダゾール−４，５−ジカルボン酸と２−エチル−４−メチルイミダゾールから成る包接化合物）
実施例１について、２ＭＺを２−エチル−４−メチルイミダゾール（以下、２Ｅ４ＭＺ）１．７６ｇへと変更した以外は同様に行い、生成物を６．７０ｇ得た。得られた生成物のＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定より、１Ｈ−イミダゾール−４，５−ジカルボン酸と２Ｅ４ＭＺがモル比として２：１で包接化された包接化合物（以下、「包接化合物Ｂ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが観測された（図２）。
[Example 2]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and 2-ethyl-4-methylimidazole)
Example 1 was performed in the same manner except that 2MZ was changed to 1.76 g of 2-ethyl-4-methylimidazole (hereinafter, 2E4MZ) to obtain 6.70 g of a product. From the XRD, TG-DSC and 1 H-NMR measurement of the obtained product, an inclusion compound (hereinafter referred to as 1H-imidazole-4,5-dicarboxylic acid and 2E4MZ was included in a molar ratio of 2: 1) It was sometimes referred to as “inclusion compound B”). The measurement results are shown below.
(XRD measurement)
The diffraction pattern of the raw material disappeared and a new diffraction pattern was observed (FIG. 2).
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸では２９３℃、２Ｅ４ＭＺでは４９℃であるのに対し、包接化合物Ｂは２４０℃であった。また重量減少のオンセット温度は２Ｅ４ＭＺでは１６２℃であるのに対し、包接化合物Ｂは２７１℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid and 49 ° C. for 2E4MZ, whereas that for inclusion compound B was 240 ° C. The onset temperature for weight reduction was 162 ° C. for 2E4MZ, whereas that for inclusion compound B was 271 ° C.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸および２Ｅ４ＭＺに帰属されるピーク積分値から、モル比が２対１で包接化されていることが分かった。
(1 H-NMR measurement)
From the peak integral values attributed to 1H-imidazole-4,5-dicarboxylic acid and 2E4MZ, it was found that the molar ratio was included at 2: 1.
[実施例３]
（１Ｈ−イミダゾール−４，５−ジカルボン酸とメタキシレンジアミンから成る包接化合物）
実施例１について２ＭＺをメタキシレンジアミン（以下、ＭＸＤＡ）４．３６ｇへと変更した以外は同様に行い生成物８．７５ｇを得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定にて１Ｈ−イミダゾール−４，５−ジカルボン酸とＭＸＤＡがモル比として１：１で包接化された包接化合物（以下、「包接化合物Ｃ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
[Example 3]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and metaxylenediamine)
Example 1 was carried out in the same manner as in Example 1 except that 2MZ was changed to 4.36 g of metaxylenediamine (hereinafter referred to as MXDA) to obtain 8.75 g of a product. The obtained product was a clathrate compound (hereinafter referred to as clathrate compound) in which 1H-imidazole-4,5-dicarboxylic acid and MXDA were clathrated at a molar ratio of 1: 1 by XRD, TG-DSC and 1 H-NMR measurement. , Sometimes referred to as “inclusion compound C”). The measurement results are shown below.
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが見られ包接化を確認した（図３）。なお、ＭＸＤＡは液状物質であり、ＸＲＤ測定はしていない。
(XRD measurement)
The diffraction pattern of the raw material disappeared, and a new diffraction pattern was observed, confirming the inclusion (FIG. 3). MXDA is a liquid substance and XRD measurement is not performed.
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸では２９３℃であるのに対して包接化合物Ｃは、１２９℃であった。また、包接化合物Ｃの重量減少に係るオンセット温度は１７６℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid, whereas that for inclusion compound C was 129 ° C. Moreover, the onset temperature which concerns on the weight reduction of the inclusion compound C was 176 degreeC.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸およびＭＸＤＡに帰属されるピーク積分値より、１Ｈ−イミダゾール−４，５−ジカルボン酸およびＭＸＤＡは１対１で包接されていることが分かった。
(1 H-NMR measurement)
From the peak integral value attributed to 1H-imidazole-4,5-dicarboxylic acid and MXDA, it was found that 1H-imidazole-4,5-dicarboxylic acid and MXDA were included in a one-to-one relationship.
[実施例４]
（１Ｈ−イミダゾール−４，５−ジカルボン酸とジイソプロピルエチルアミンから成る包接化合物）
実施例１について２ＭＺをジイソプロピルエチルアミン（以下、ＤＩＥＡ）４．１３ｇへと変更した以外は同様に行い生成物８．１１ｇを得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定にて１Ｈ−イミダゾール−４，５−ジカルボン酸とＤＩＥＡがモル比として１：２で包接化された包接化合物（以下、「包接化合物Ｄ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
[Example 4]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and diisopropylethylamine)
Example 1 was carried out in the same manner except that 2MZ was changed to 4.13 g of diisopropylethylamine (hereinafter referred to as DIEA) to obtain 8.11 g of a product. The obtained product was an inclusion compound (hereinafter referred to as an inclusion compound) in which 1H-imidazole-4,5-dicarboxylic acid and DIEA were included in a molar ratio of 1: 2 by XRD, TG-DSC and 1 H-NMR measurement. , Sometimes referred to as “inclusion compound D”). The measurement results are shown below.
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが見られ包接化を確認した（図４）。なお、ＤＩＥＡは液状物質であり、ＸＲＤ測定はしていない。
(XRD measurement)
The diffraction pattern of the raw material disappeared and a new diffraction pattern was observed, confirming the inclusion (FIG. 4). DIEA is a liquid substance and XRD measurement is not performed.
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸では２９３℃であるのに対して包接化合物Ｄは、１６１℃であった。また、包接化合物Ｄの重量減少に係るオンセット温度は１６０℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid, whereas that for inclusion compound D was 161 ° C. Moreover, the onset temperature which concerns on the weight reduction of the inclusion compound D was 160 degreeC.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸およびＤＩＥＡに帰属されるピーク積分値より、１Ｈ−イミダゾール−４，５−ジカルボン酸およびＤＩＥＡは１対２で包接されていることが分かった。
(1 H-NMR measurement)
From the peak integration value attributed to 1H-imidazole-4,5-dicarboxylic acid and DIEA, it was found that 1H-imidazole-4,5-dicarboxylic acid and DIEA were included in a 1: 2.
[実施例５]
（１Ｈ−イミダゾール−４，５−ジカルボン酸とジエチレントリアミンから成る包接化合物）
実施例１について２ＭＺをジエチレントリアミン（以下、ＤＥＴＡ）３．３０ｇへと変更した以外は同様に行い生成物７．６７ｇを得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定にて１Ｈ−イミダゾール−４，５−ジカルボン酸とＤＥＴＡがモル比として１：１で包接化された包接化合物（以下、「包接化合物Ｅ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
[Example 5]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and diethylenetriamine)
Example 1 was carried out in the same manner as in Example 1 except that 2MZ was changed to 3.30 g of diethylenetriamine (hereinafter referred to as DETA) to obtain 7.67 g of a product. The obtained product was a clathrate compound (hereinafter referred to as clathrate compound) in which 1H-imidazole-4,5-dicarboxylic acid and DETA were clathrated at a molar ratio of 1: 1 by XRD, TG-DSC and 1 H-NMR measurement. , Sometimes referred to as “inclusion compound E”). The measurement results are shown below.
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが見られ包接化を確認した（図５）。なお、ＤＥＴＡは液状物質であり、ＸＲＤ測定はしていない。
(XRD measurement)
The diffraction pattern of the raw material disappeared, and a new diffraction pattern was observed, confirming inclusion (FIG. 5). Note that DETA is a liquid substance and XRD measurement is not performed.
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸では２９３℃であるのに対して包接化合物Ｅは、２６７℃であった。また、包接化合物Ｅの重量減少に係るオンセット温度は２７３℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid, whereas that for inclusion compound E was 267 ° C. Moreover, the onset temperature concerning the weight reduction of the inclusion compound E was 273 degreeC.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸およびＤＥＴＡに帰属されるピーク積分値より、１Ｈ−イミダゾール−４，５−ジカルボン酸およびＤＥＴＡは１対１で包接されていることが分かった。
(1 H-NMR measurement)
From the peak integral value attributed to 1H-imidazole-4,5-dicarboxylic acid and DETA, it was found that 1H-imidazole-4,5-dicarboxylic acid and DETA were included in a one-to-one relationship.
[実施例６]
（１Ｈ−イミダゾール−４，５−ジカルボン酸と１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エンから成る包接化合物）
実施例１について２ＭＺを１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（以下、ＤＢＵ）４．８７ｇへと変更した以外は同様に行い生成物８．５３ｇを得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定にて１Ｈ−イミダゾール−４，５−ジカルボン酸とＤＢＵがモル比として１：１で包接化された包接化合物（以下、「包接化合物Ｆ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
[Example 6]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and 1,8-diazabicyclo [5.4.0] undec-7-ene)
Except that 2MZ was changed to 4.87 g of 1,8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as DBU) for Example 1, 8.53 g of product was obtained. The obtained product was an inclusion compound in which 1H-imidazole-4,5-dicarboxylic acid and DBU were included at a molar ratio of 1: 1 by XRD, TG-DSC and 1 H-NMR measurement (hereinafter referred to as “the inclusion compound”). , Sometimes referred to as “inclusion compound F”). The measurement results are shown below.
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが見られ包接化を確認した（図６）。なお、ＤＢＵは液状物質であり、ＸＲＤ測定はしていない。
(XRD measurement)
The diffraction pattern of the raw material disappeared, and a new diffraction pattern was observed, confirming inclusion (FIG. 6). Note that DBU is a liquid substance and XRD measurement is not performed.
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸では２９３℃であるのに対して包接化合物Ｆは、２０９℃であった。また、包接化合物Ｆの重量減少に係るオンセット温度は２６８℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid, whereas inclusion compound F was 209 ° C. Moreover, the onset temperature concerning the weight reduction of the clathrate compound F was 268 degreeC.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸およびＤＢＵに帰属されるピーク積分値より、１Ｈ−イミダゾール−４，５−ジカルボン酸およびＤＢＵは１対１で包接されていることが分かった。
(1 H-NMR measurement)
From the peak integral value attributed to 1H-imidazole-4,5-dicarboxylic acid and DBU, it was found that 1H-imidazole-4,5-dicarboxylic acid and DBU were included in a one-to-one relationship.
[実施例７]
（１Ｈ−イミダゾール−４，５−ジカルボン酸と２−フェニルイミダゾリンから成る包接化合物）
実施例１について２ＭＺを２−フェニルイミダゾリン（以下、２ＰＺＬ）４．６８ｇへと変更した以外は同様に行い生成物９．１３ｇを得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定にて１Ｈ−イミダゾール−４，５−ジカルボン酸と２ＰＺＬがモル比として１：１で包接化された包接化合物（以下、「包接化合物Ｇ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
[Example 7]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and 2-phenylimidazoline)
Example 1 was carried out in the same manner except that 2MZ was changed to 2.68 g of 2-phenylimidazoline (hereinafter 2PZL) to obtain 9.13 g of a product. The obtained product was an inclusion compound in which 1H-imidazole-4,5-dicarboxylic acid and 2PZL were included in a molar ratio of 1: 1 by XRD, TG-DSC and 1 H-NMR measurement (hereinafter referred to as “inclusion compound”). , Sometimes referred to as “inclusion compound G”). The measurement results are shown below.
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが見られ包接化を確認した（図７）。
(XRD measurement)
The diffraction pattern of the raw material disappeared, and a new diffraction pattern was observed, confirming inclusion (FIG. 7).
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸は２９３℃、２ＰＺＬは９９℃であるのに対して、包接化合物Ｇは２５３℃であった。また、重量減少に係るオンセット温度は２ＰＺＬで１７４℃であるのに対して、包接化合物Ｇでは２６４℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid and 99 ° C. for 2PZL, whereas that for inclusion compound G was 253 ° C. The onset temperature for weight reduction was 174 ° C. for 2PZL, whereas it was 264 ° C. for inclusion compound G.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸および２ＰＺＬに帰属されるピーク積分値より、１Ｈ−イミダゾール−４，５−ジカルボン酸および２ＰＺＬは１対１で包接されていることが分かった。
(1 H-NMR measurement)
From the peak integral values attributed to 1H-imidazole-4,5-dicarboxylic acid and 2PZL, it was found that 1H-imidazole-4,5-dicarboxylic acid and 2PZL were included in a one-to-one relationship.
[実施例８]
（１Ｈ−イミダゾール−４，５−ジカルボン酸と２−メチルイミダゾリンから成る包接化合物）
実施例１について２ＭＺを２−メチルイミダゾリン（以下、２ＭＺＬ）２．６９ｇへと変更した以外は同様に行い生成物７．３７ｇを得た。得られた生成物は、ＸＲＤ、ＴＧ−ＤＳＣ及び１Ｈ−ＮＭＲ測定にて１Ｈ−イミダゾール−４，５−ジカルボン酸と２ＭＺＬがモル比として１：１で包接化された包接化合物（以下、「包接化合物Ｈ」と言うことがある。）であることを確認した。以下にその測定結果を示した。
[Example 8]
(Inclusion compound comprising 1H-imidazole-4,5-dicarboxylic acid and 2-methylimidazoline)
Example 1 was carried out in the same manner except that 2MZ was changed to 2.69 g of 2-methylimidazoline (hereinafter, 2MZL) to obtain 7.37 g of a product. The obtained product was an inclusion compound in which 1H-imidazole-4,5-dicarboxylic acid and 2MZL were included in a molar ratio of 1: 1 by XRD, TG-DSC and 1 H-NMR measurement (hereinafter referred to as “inclusion compound”). , Sometimes referred to as “inclusion compound H”). The measurement results are shown below.
（ＸＲＤ測定）
原料の回折パターンが消失し、新規の回折パターンが見られ包接化を確認した（図８）。
(XRD measurement)
The diffraction pattern of the raw material disappeared, and a new diffraction pattern was observed, confirming inclusion (FIG. 8).
（ＴＧ−ＤＳＣ測定）
融解に伴う吸熱ピークのオンセット温度は、１Ｈ−イミダゾール−４，５−ジカルボン酸は２９３℃、２ＭＺＬは８８℃であるのに対して、包接化合物Ｈは２７３℃であった。また、重量減少に係るオンセット温度は２ＭＺＬで１０１℃であるのに対して、包接化合物Ｈでは２６４℃であった。
(TG-DSC measurement)
The onset temperature of the endothermic peak accompanying melting was 293 ° C. for 1H-imidazole-4,5-dicarboxylic acid, and 88 ° C. for 2MZL, whereas the inclusion compound H was 273 ° C. The onset temperature related to weight reduction was 101 ° C. at 2 MZL, whereas it was 264 ° C. for inclusion compound H.
（１Ｈ−ＮＭＲ測定）
１Ｈ−イミダゾール−４，５−ジカルボン酸および２ＭＺＬに帰属されるピーク積分値より、１Ｈ−イミダゾール−４，５−ジカルボン酸および２ＭＺＬは１対１で包接されていることが分かった。
(1 H-NMR measurement)
From the peak integral values attributed to 1H-imidazole-4,5-dicarboxylic acid and 2MZL, it was found that 1H-imidazole-4,5-dicarboxylic acid and 2MZL were included in a one-to-one relationship.
（２）硬化特性試験
実施例１で得られた包接化合物Ａの硬化特性を確認した。比較に、２ＭＺ単体、１Ｈ−イミダゾール−４，５−ジカルボン酸単体、及び２ＭＺと１Ｈ−イミダゾール−４，５−ジカルボン酸の混合物を用いた。
[実施例９]
（エポキシ硬化樹脂形成用組成物の調製）
エポキシ樹脂（商品名：エポトート（登録商標）ＹＤ−１２８、東邦化成（株）製）５ｇに対して、２００ｍｇ（４ｐｈｒ）の包接化合物Ａを添加した後、２５℃で１０分間混練することで、エポキシ硬化樹脂形成用組成物Ａを得た。
（エポキシ硬化樹脂形成用組成物のＤＳＣ測定）
ＤＳＣ測定装置（ＤＳＣ１、メトラー・トレド社製）を用い、アルミ容器内に約５〜１０ｍｇになるようエポキシ硬化樹脂形成用組成物Ａを量りとり、窒素パージ下（窒素の流速：５０ｍＬ／ｍｉｎ）、３０℃から２５０℃まで昇温（昇温速度：１０ｋ／ｍｉｎ）を行い、エポキシ硬化樹脂形成用組成物Ａの硬化反応に基づく発熱挙動を追跡した。横軸に時間及び温度を採った測定結果を図９に示した。
(2) Curing property test The curing property of the inclusion compound A obtained in Example 1 was confirmed. For comparison, 2MZ simple substance, 1H-imidazole-4,5-dicarboxylic acid simple substance, and a mixture of 2MZ and 1H-imidazole-4,5-dicarboxylic acid were used.
[Example 9]
(Preparation of composition for forming epoxy cured resin)
By adding 200 mg (4 phr) of inclusion compound A to 5 g of epoxy resin (trade name: Epototo (registered trademark) YD-128, manufactured by Toho Kasei Co., Ltd.), kneading at 25 ° C. for 10 minutes. An epoxy cured resin forming composition A was obtained.
(DSC measurement of epoxy cured resin forming composition)
Using a DSC measuring device (DSC1, manufactured by METTLER TOLEDO), weigh the composition A for forming an epoxy cured resin in an aluminum container so as to be about 5 to 10 mg, and under a nitrogen purge (nitrogen flow rate: 50 mL / min) The temperature was raised from 30 ° C. to 250 ° C. (temperature increase rate: 10 k / min), and the exothermic behavior based on the curing reaction of the epoxy cured resin forming composition A was followed. The measurement results with time and temperature on the horizontal axis are shown in FIG.
［比較例１］
（エポキシ硬化樹脂形成用組成物の調製）
実施例９のエポキシ硬化樹脂形成用組成物の調製について、包接化合物Ａを２ＭＺ ２００ｍｇへと変更した以外は同様に行い、２ＭＺから成るエポキシ硬化樹脂形成用組成物を得た。
（エポキシ硬化樹脂形成用組成物のＤＳＣ測定）
実施例９のエポキシ硬化樹脂形成用組成物のＤＳＣ測定について、エポキシ硬化樹脂形成用組成物Ａを２ＭＺから成るエポキシ硬化樹脂形成用組成物へと変更した以外は同様に行い、硬化反応に基づく発熱挙動を追跡した。その結果を図９に示した。
[Comparative Example 1]
(Preparation of composition for forming epoxy cured resin)
The preparation of the epoxy cured resin forming composition of Example 9 was performed in the same manner except that the inclusion compound A was changed to 200 mg of 2MZ to obtain an epoxy cured resin forming composition comprising 2MZ.
(DSC measurement of epoxy cured resin forming composition)
The DSC measurement of the epoxy cured resin forming composition of Example 9 was performed in the same manner except that the epoxy cured resin forming composition A was changed to an epoxy cured resin forming composition composed of 2MZ, and heat generation based on the curing reaction. The behavior was tracked. The results are shown in FIG.
［比較例２］
（エポキシ硬化樹脂形成用組成物の調製）
実施例９のエポキシ硬化樹脂形成用組成物の調製について、包接化合物Ａを１Ｈ−イミダゾール−４，５−ジカルボン酸２００ｍｇへと変更した以外は同様に行い、１Ｈ−イミダゾール−４，５−ジカルボン酸から成るエポキシ硬化樹脂形成用組成物を得た。
（エポキシ硬化樹脂形成用組成物のＤＳＣ測定）
実施例９のエポキシ硬化樹脂形成用組成物のＤＳＣ測定について、エポキシ硬化樹脂形成用組成物Ａを１Ｈ−イミダゾール−４，５−ジカルボン酸から成るエポキシ硬化樹脂形成用組成物へと変更した以外は同様に行い、硬化反応に基づく発熱挙動を追跡した。その結果を図９に示した。
[Comparative Example 2]
(Preparation of composition for forming epoxy cured resin)
The preparation of the epoxy cured resin forming composition of Example 9 was performed in the same manner except that the inclusion compound A was changed to 200 mg of 1H-imidazole-4,5-dicarboxylic acid, and 1H-imidazole-4,5-dicarboxylic acid. An epoxy cured resin forming composition comprising an acid was obtained.
(DSC measurement of epoxy cured resin forming composition)
About the DSC measurement of the epoxy cured resin forming composition of Example 9, except that the epoxy cured resin forming composition A was changed to an epoxy cured resin forming composition comprising 1H-imidazole-4,5-dicarboxylic acid. In the same manner, the exothermic behavior based on the curing reaction was followed. The results are shown in FIG.
［比較例３］
（エポキシ硬化樹脂形成用組成物の調製）
実施例９のエポキシ硬化樹脂形成用組成物の調製について、包接化合物Ａの代わりに１Ｈ−イミダゾール−４，５−ジカルボン酸 １３１ｍｇと、２ＭＺ ６９ｍｇをそれぞれ包接化操作せずに添加した以外は同様に行い、未包接化体から成るエポキシ硬化樹脂形成用組成物を得た。
（エポキシ硬化樹脂形成用組成物のＤＳＣ測定）
実施例９のエポキシ硬化樹脂形成用組成物のＤＳＣ測定について、エポキシ硬化樹脂形成用組成物Ａを未包接体から成るエポキシ硬化樹脂形成用組成物へと変更した以外は同様に行い、硬化反応に基づく発熱挙動を追跡した。その結果を図９に示した。
[Comparative Example 3]
(Preparation of composition for forming epoxy cured resin)
For the preparation of the epoxy cured resin forming composition of Example 9, 131 mg of 1H-imidazole-4,5-dicarboxylic acid and 69 mg of 2MZ were added in place of the inclusion compound A without inclusion operation. It carried out similarly and obtained the composition for epoxy cured resin formation which consists of a non-inclusion body.
(DSC measurement of epoxy cured resin forming composition)
The DSC measurement of the epoxy cured resin forming composition of Example 9 was carried out in the same manner except that the epoxy cured resin forming composition A was changed to an epoxy cured resin forming composition consisting of non-inclusion bodies. The exothermic behavior based on was tracked. The results are shown in FIG.
実施例９は、比較例１と比較して、エポキシ硬化に伴う発熱ピークが高温側へとシフトしており、包接化により２ＭＺの熱的安定性が向上した。また比較例２と比較すると、実施例９の発熱ピークは低温側へシフトし、その形状は非常にシャープなものへと変化し、包接化により１Ｈ−イミダゾール−４，５−ジカルボン酸の硬化活性が向上した。
さらに、包接化操作をせずに１Ｈ−イミダゾール−４，５−ジカルボン酸と２ＭＺをただ添加した未包接体の比較例３では、２成分の実質的な添加量は実施例９と同じであるにも関わらず、発熱ピークはブロード化し、硬化特性は著しく悪化した。以上より、硬化特性の改善には単純な２成分の混合では不可能であり、包接化操作の有用性が明らかとなった。
In Example 9, as compared with Comparative Example 1, the exothermic peak accompanying epoxy curing was shifted to a high temperature side, and the thermal stability of 2MZ was improved by inclusion. Further, compared with Comparative Example 2, the exothermic peak of Example 9 shifted to a low temperature side, the shape thereof changed to a very sharp one, and the 1H-imidazole-4,5-dicarboxylic acid was cured by inclusion. Activity improved.
Further, in Comparative Example 3 of the non-inclusion body in which only 1H-imidazole-4,5-dicarboxylic acid and 2MZ were added without performing the inclusion operation, the substantial addition amount of the two components was the same as in Example 9. Nevertheless, the exothermic peak was broadened and the curing characteristics were significantly deteriorated. From the above, it was impossible to improve the curing characteristics by simply mixing two components, and the usefulness of the inclusion operation became clear.
Claims (5)
成分（１）：１Ｈ−イミダゾール−４，５−ジカルボン酸
成分（２）：脂肪族アミン類、環状アミン類、芳香族アミン類、イミダゾリン系化合物及びイミダゾール系化合物からなる群より選ばれる少なくとも１種 An inclusion compound containing the following component (1) and component (2).
Component (1): 1H-imidazole-4,5-dicarboxylic acid component (2): at least one selected from the group consisting of aliphatic amines, cyclic amines, aromatic amines, imidazoline compounds and imidazole compounds
An epoxy cured resin obtained by curing the composition for forming an epoxy cured resin according to claim 3 by heat treatment.
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| JP2017049398A JP2018150485A (en) | 2017-03-15 | 2017-03-15 | Clathrate compound |
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| JP2017049398A JP2018150485A (en) | 2017-03-15 | 2017-03-15 | Clathrate compound |
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